Preparation of metal sulfonate composition



, bitumen to wet mineral aggregates.

Patented Apr. 13, 1954 PREPARATION or METAL SULFONATE COMPOSITION Frederick W. Schuessler, Valparaiso, Ind., and Thomas J. Wishlinski, Lansing, 111., assignors to Standard Oil Company, Chicago, 111., a corporation of Indiana No Drawing.

Application August 30, 1951,

Serial No. 244,476

6 Claims. (Cl-'106-285) This invention relates to an improved process for manufacturing petroleum sulfonate compositions and bituminous compositions containing same. More particularly, it relates to an' improved process whereby superior metal sulfonatecontaining adjuncts for bituminous coating materials may be prepared from selected portions of sulfuric acid sludges resulting from the treatment of mineral oils with concentrated or fuming sulfuric acid.

Bituminous materials, such as normally liquid road oils and normally liquid to normally solid asphalts, are frequently compounded with various adjuncts to improve the adhesiveness of the-bitumen to wet mineral aggregates. Among the various adjuncts employed for this purpose are those comprising soaps of sulfonic acids, particularly the alkaline earth metal and heavy metal soaps of sulfonic acids obtained in the treatment of hydrocarbon oils with concentrated or fuming sulfuric acid. One source of such sulfonic acids is the sludge obtained in the treatment of hydrocarbon oils with sulfuric acid of about 95 per cent strength or above, and preferably fuming sulfuric acid. It is an object of the present invention to provide a method of preparing stable,

' homogenous adjuncts for incorporation in paving asphalts and the like containing water-insoluble sludge acid soaps.

A further object of the invention is to provide a method of preparing a superior metal sulfonate containing adjunct for bituminous materials which comprises an aromatic hydrocarbon and water-insoluble metal sulfonates derived from sulfuric acid sludge, said adjunct being stable and homogeneous.

Still another object of the invention is to.prc vide a method of preparing a stable homogeneous adjunct for addition to paving bitumens which comprises a substantial proportion of a waterinsoluble metal sulfonate obtained from an acid sludge, resulting from the treatment of a hydrocarbon ,oil with concentrated or fuming sulfuric acid, which adjunct displays an exceptionally effective ability to promote the adherance of Other o jects and advantages of the present invention will become apparent from the following description.

It has been discovered previously by our coworkers that a composition comprising the waterinsoluble metal soaps ,of preferentiallywatersoluble sulfonic acids derived from acid sludge,

an aromatic hydrocarbon, alcohol, a small amount of water and some mineral oil is particularly suitable as an adjunct for bituminous paving materials. Such a novel composition and a method of preparing same are described in copending application for Letters Patent Serial No. 108,428, filed August 3, 1949. A distinguishing feature of the present invention resides in the use of preferentially water-soluble sulfonic acids from only a selected portion of a sulfuric acid sludge rather than from a total sludge.

Briefly stated, a novel process is described in the copending application wherein a sludge resulting from acid treatment of a technical white oil or the like with concentrated or fuming sulfuric acid is substantially freed of unreacted sulfuric acid and then diluted with more than about 3 volumes of water for each volume of liver and mixed with suiiicient basic compound to neutralize the sulfonic acids present therein; precipitated sulfonates are then mixed with an arcmatic hydrocarbon, sufficient base added to neutralize any occluded acidic material, following which the aromatic hydrocarbon-sulfonate mixture is dehydrated and there is added to the dehydrated mixture from about 2 per cent to 15 per cent of an aliphatic alcohol. That process usually results in stable homogeneous sulfonate compositions of good coating ability but it has been found that such compositions are at times unstable, settle in a non-homogeneous two phase mixture andare inferior in ability to promote wet aggregate coating.

It has now been discovered that such dificulties can readily be eliminated and a superior adjunct can be consistently produced if the sludge is settled and the lower portion drawn off and discarded before the hydrolysis step. The sludge sludge. As the sludge settles from the oil a predominant amount of the so-called blackacids present therein stratify in the lower portion of the sludge.

The blackacids are the most water soluble ofthe petroleum sulfonicacids found in sludge water for eaoh-"volume of" liver.

liver is then heated. to" a temperature of from and are insoluble in chloroform, naphtha, benzene, etc. When a complex mixture of sulfonates derived from sludge, said mixture containing mahogany soaps, green acid soaps, and black acid soaps, is mixed and shaken with chloroform and a 3:1 hydrochloric acid solution (i. e., a solution prepared by mixing 3 volumes of water with 1 volume-of. concentrated acid) a twophase system results upon settling in which the chloroform, containing sulfonates other than the black acid sulfonates, comprises the lower phase and hydrochloric acid comprises the upper phase with substantially all of the black acid scapsconcentrated at the interface of the two solvents.

The black acids stratifyirom the less watersoluble sludge acids andtmay' -be removed-to a substantial extent by drawing off the 'lOWEI' to 60 per cent of the sludge and discarding the same. Depending to some extent upon the type of oil being treated and the sulfuric aGidL-treating level at which the sludge is obtainedythe formation of two distinct phases may orzmayinot take place. The more fluid the sludge the greater 1 likelihood I of vtwo phases, .in which case. removal of the lower liquid. .phase will remove most of .the black acids. cutphase separation, however, most-of the/black A acids; after the sludge has settled, will be present ,inthe lower portion of the sludge and =may be With .or without: such. a :clear readilydrawn off. Theprocess is then .carried out employing only .the top portion which is low in black acids and .a homogeneousadjunct is I readily prepared whichis particularly-eifective as an additive-in road .oils .and .asphalts-for. pro- .moting coating of wet aggregates.

In accordance with the present invention the stable homogeneous composition containing .a water-insoluble metal salt of sulfonic acids .derived from acid sludge resulting from-the treatment of hydrocarbon .oils such "as lubricating I oil 1 distillates, with sulfuric acidofat least 95 per about 0.5 to 9.0 pounds of. acid per gallon of oil, is settledafter each dump and the top. layer from each Stratification is combinedtina'total mix and hydrolyzed or r the sludge from each dump .-.may

be combined and-the draw-off madefrom .the

total sludge vafter .-a sufiicient settlingcperiod. Following-hydrolysis the mix is= settled once again to permit separation of the weaksulf-uricacid layer resulting from the hydrolysis. I After withdrawing theweaksulfuric acid layer theremainder" of hydrolyzed mix; commonly. referred togas liver,.-is 'diluted with -:water. It is important -;that:the "liver= besuflicientlydiluted with water at this point prior to the:neutralization step,since in a properly diluted liver the metalsulfonate formed .upon neutralization: is preferentially precipitated rather than'th metalsulfateithusre- "sulting in a metal sulfonate of low inorganic salt content. "The dilution required to obtain the preferential: precipitation of the metal sulfonate is dependent upon the concentration of 'sulfonic acid and sulfuric acid inthe liver. In general,

the "liver,,- or separated hydrolyzed sludge,

: should be diluted with morethan about3 volumes barium or aheavy poly-valentmetal such as lead, iron, zinc, copper, cobalt, manganese, etc, al-

though the alkaline earth metals, particularly calcium are preferred. Other suitable neutralizing agents are basic nitrogenous compounds.

' Thcneutralizingagent is preferably added in the "form of a slurry and the reacting mixture agitatedsuch .asby. air blowing to accelerate the reaction 1 and prevent excessive settling of the uneutralizing agent. After the desired amount of .,.the'neutralizing-z agent has been added, the precipitated metal sulfonate is allowed to settle end-thesupernatant liquid drawn oil, the arcmatic hydrocarbon of the type hereinafter disclosedissadded to the crude sulfonate mixture in amounts of from about per cent to about 75 .--per cent by -weiglit, and preferably. .from ve. -bout per cent to about 60 perv cent byweight .After the crude sulfonate-and the aromatichydrocarbonare well mixed, sufficient neutralizing. agent is added to completelyneutralize.the. residual acidityof the material. The neutralized. mixture of sulfonate and aromatic hydrocarbon. is dehydrated-to lower the :watercontentto-from about 1 per cent to. about 35 percent and preierablyirom about 3 per cent to about 10 per cent.

The extent to-v which theneutralized..product is dehydrated will. depend-to some extent upon the ,type of falcohol used. For. example-when using alcohols of up to .aboutfive carbon-atoms dehydration to a watercontent-of from. about 1 percent to 31301113110 percent is-.desirable,-where- 40,

' pe, nonyl alcohol, cetyl alcohol, etc., dehydraas-when using higher alcohols, such-as, for exam- .tion to a water content of-about35percent will .be sufficient toprevent phase separation. The dehydrated mixture is cooled-to a temperature of at least about .1-- F. and the mixture... diluted withfrom about 2 percentto about-l5 per cent, and preferably from: about. 4-per cent to-about 8 per cent of .the' aliphaticalcohol. After: settling -to remove excess amounts of -inorganice-salts,

which may still be present, the Imixture-is ready for'storage, or forrcompounding'with the :bituminous material.

. It :is imp'ortantthat'the'finished mixture contain no more than .the. maximum amount. of water -indicated above since *the presence oilarger amounts of water-will increase the'dangerof phase separation of water, alcohol andsoapmixture from the aromatic hydrocarbon. However,

when the amount of water present-zisxmaintained within 1 the aboveementioned limitsi a. stable ho- *mogeneous product 'is' obtained.

uThesulfonate 'composition obtained in the manner described contains essentially the fellowof water, and preferably at least 5 volumes of The diluted Hydrocarbon oil ing components in the following approximate proportions:

Preferred Range (Percent) Range (Percent) Metal sulfonate Aromatic hydrocarbon Aliphatic alcohol. Water Aromatic hydrocarbons" suitable for use "in accordance with the present invention are prefer ably those having a boiling point above about 220 F. at atmospheric pressures and includes mono-nuclear aromatic hydrocarbons, such as the xylenes, and poly-nuclear or condensed ring aromatics, such as naphthalenes, alkylated naphthalenes, such as methylated naphthalenes and ethylated naphthalenes, and mixtures of the higher boiling mono-nuclear aromatic hydrocarbons and poly-nuclear hydrocarbons.

A preferred source of mixed aromatic hydrocarbons suitable for use in the present invention is a light catalytic cycle stock obtained from a catalytic hydrocarbon cracking operation in which gas oil or heavier hydrocarbons, such as reduced crude, are cracked at a temperature of about 800 F. to 1050 F. at a pressure of about atmospheric to 50 pounds per square inch in the presence of suitable catalysts, such as for example, silica-alumina, silica-magnesia and other well-known cracking catalysts. A method of conducting a fluidized catalytic cracking operation is described in U. S. Pat. 2,341,193, issued to Fred W. Scheineman, February 8, 1944. The fraction suitable for use in the present invention is a heavier-than-gasoline fraction usually recycled to cracking. These fractions, depending upon their boiling range, are commonly referred to as light cycle stock and heavy cycle stock. 7 A catalytic light cycle stock particularly well suited for this invention is a fraction having an arcmatic content of at least about 40 to about 50 percent, and a distillation range between about 425 F. and about 560 F. A typical analysis of a suitable light catalytic cycle stock shows the material to be composed substantially of about 10 per cent normal 012 to C paraffins, about per cent of other paraffins and naphthenes, about 5 per cent mono-nuclear aromatics which are mainly monoto hexa-alkylated benzenes, and about 40 per cent poly-nuclear aromatics which are main y alkyl naphthalenes, largely methylated naphthalenes. A typical light catalytic cycle stock will give the following A. S. T. M. distillation:

Initial boiling point F 430 10% over F 448 over F 4'78 over F 518 Maximum boiling point F 552 While we prefer to use a light cycle stock from a cata ytic cracking operation of the type abovedescribed. hydrocarbon fractions from other catalytic hydrocarbon conversion processes or thermal hydrocarbon conversion processes are suitable provided they have a sufficiently high aromati ccontent, at least 40 to 50 per cent, and have suitable disti lation characteristics, 1. e. boiling above about 220 F.

In place of using the Whole catalytic cycle stock we may extract the aromatic components from the cycle stock and use the aromatic extract.

The aromatics may be extracted by extraction with the usual and known solvents, such as for example, liquid hydrogen fluoride, nitromethane, liquid sulfur dioxide, etc.

Other mixed aromatic hydrocarbons suitable for use in the present invention are mixtures of aromatic hydrocarbons produced by the catalytic conversion of aliphatic hydrocarbons by the socalled hydroforming process. This mixture is known in thepetroleum refining artas (catalytic reform naphtha bottoms, hydroformer polymers, or "hydroformer bottoms. They will be referred to hereinafter as hydroformer polymers. A process by which the hydroformer polymers are obtained is described in U. S. Patent No. 2,320,147. Briefly, the process comprises treating virgin or cracked naphtha or mixtures thereof with a solid porous hydroforming catalyst such as an oxide of a metal of group II to IV of the periodic system, such as the oxide of chromium or molybdenum, suitably supported on alumina or magnesia. The conversion is suitably carried out at a temperature of 850 F. to 1050 F. and, if desired, in the presence of hydrogen. The hydroformer products are fractionated by taking overhead a catalytically reformed gasoline of suitable end point and recovering the higher boiling materials as bottoms, which boil from about 400 F. to about 750 F., and have gravities of from about 10 API to about 18 API. A typical vacuum distillation of a hydroformer sample having a gravity of about 12 API shows the following composition:

Fraction Components Toluene.

Xylenes. 1,3,5-Trimethylbcnzenes. 1,3,4-Trimethylbenzene. 1.2,3-Trimethylbonzene. Tetramcthylbenezenc. Naphthalenes. Monomethylnaphthalenes. Diphenyl.

Dimethylnapthalenes. Methyldiphenyls. 'Irimethylnapthalenes.

Fluorene.

Mcthylfluorenes. Anthracene and Phenanthrene.

Pyrene. Tetracycllcs and Higher.

A representative hydroformer bottoms fraction exhibits the following physical properties:

Either the entire hydroformer polymer or lower boiling fractions thereof, such as the 0 to 90 per cent fraction boiling between about 400 F. and 600 F. or the 0 to 50 per cent fraction boiling between about 400 F. and 500 F. may be used.

The alcohol employed in the present invention is an aliphatic alcohol, such as for example, ethyl alcohol, propyl alcohol, isopro-pyl alcohol, butyl alcohol, and amyl alcohols, such as tertiary amyl aicohol. Higher alcohols of 9 to 16 carbon atoms and higher are not precluded; nonyl alcohol has been found to be operable.

While the preferentially water-soluble sulfonic acids employed in this invention may be obtained from acid sludges resulting from the treatment I of viscous hydrocarbon oils having Saybolt Universal viscosity of from 80 seconds to 900 seconds at F. with 0.5 to 9 pounds of concentrated or fuming sulfuric acid per gallon of oil being Methylanthracenes and Methylphenanthrenes.

treated, it ispreferred to-employ theacid-sludges obtained in the treatment of hydrocarbon oils .With 2.120 4 pounds of fuming sulfuric acid per gallon of oil being treated.

The present invention will bemore fully described and understood by reference to the following specific examples which are illustrative and in no way intended to limit the scope of the invention.

Ezcample I Ten gallons of naphthenic Kittrell Stanolind distillate, having a viscosity of 720 SSU at 100 F., a flash point of 380 F., API gravity of 21.3 and a pour point of 5 F. were treated with one-half pound dumps of fuming H2304 (104.5%) per gallon of oil to a total of 2.5 pounds of acid per gallon of oil. Th sludge was permitted to settle from the oi after each dump. 0f the 2.5 poundsludge, approximately the lower 60% was drawn oil and separated from the top Both portions were hydrolyzed separately by mixing with water and live steam until the H2804 present was reduced to a concentration of about 30%. li he separated weak H2804 was discarded in each case and the livers analyzed. The black acid content of the liver prepared from the lower sludge portion was found to constitute 7'? of the total sulfonates present in the liver. The black acid content of theliver prepared from the top 40% sludge portion was found to constitute only 28% of the total sulfonates in the liver.

Two hundred grams of the liver resulting from the top 40% portion of the sludge were diluted with 5 volumes of water and neutralized by adding 26.4 grams Ca(OH)z in the form of an aqueous slurry to precipitate the calcium soaps of the sulfonic acids. 157 grams of light catalytic cycle stock were added .to the soap after the supernatant solution had been decanted. Since the mixture gave an alkaline reaction, no further neutralization was necessary and the mixture was dehydrated to a water content of about 3%. The viscosity of the mixture was adjusted by the addition of 15 cc. of isopropyl alcohol. The additive thus prepared when added in 2 per cent concentration to a cut bacl: asphalt resulted in superior coating of wet aggregate. The liver obtained by hydrolyzing the bottom portion of the sludge defied processing and could not be 7 Example II A technical white. oil sludge. at the. 215" pound Y level wassettlcd and 2,700 gallons (37%) were withdrawn from the bottom and discarded and the remaining portion was then hydrolyzed. At the 3.0 pound treating level, a sludge was again settled and the lower 2,700 gallons (39%) thereof were withdrawn and discarded and the upper portion was hydrolyzed in the weak acid-liver mix resulting from hydrolysis of the 2.5 pound sludge. After settling, the weak acid resulting from hydrolysis was separated and discarded. In the laboratory 500 cc. of the combined liver were then diluted with 2,500 cc. of water and sufli'cient lime slurry (74 grams of lime)was. added to totally neutralize, all acidity andto precipitate calcium sulfonates- 1.00 grams of the precipitated soap were .added to cc. of. light and aggregate.

catalytic cycle stock and: the mixture was dehydrated to 2.3% water. Approximately 10% of isopropanol was added to adjust the viscosity. During the dehydration step, no phase .separation occurred between sulfonate and cycle-stock and there was at all times an easily handled system which was stable and homogeneous. Attempts to prepare an adjunct from a total. sludge of: suchanoil under similar conditions resulted in a mixture which was diffi0111l3,,if notimpossible, to handle because of separation between aromatic and soap during the dehydrationstep.

Example III A combined liver was prepared ina manner similar to that described in Example II, above. Portions of 2.5 pound and 3.0 pound technical White oil sludges were used. The lower 2,600 gallons (40%) of the 2.5 pound sludge were, removed and discarded. and the upper remaining portion was hydrolyzed in 10,000 gallons of water. The same amount of a total 3.0 pound sludge having identical volume was withdrawn and discarded-as in the case ofthe 2.5 pound. sludge and the top portion was hydrolyzed in the liverweak acid mixture resulting from the first hydrolysis. After settling, the weak acid resulting from the hydrolysis was separated from the liver and the liver was diluted with 81,500 gallons (approximately 5:1) of water and neutralized with 16,250 pounds of lime in water slurry. After settling, the supernatantwater phase was discarded and 0.8 volume of light catalytic cycle stock was added to the precipitated soap, The resulting mixture was then dehydrated to 4.9% water. Approximately 1,800 gallons of isopropanel were added for final viscosity adjustment. Processing was smooth with no phase separation during the dehydrationstep and the adjunct thus prepared exhibited excellent coating properties, as indicated in Table I.

The sulfonate composition of the herein described invention is especially well-suited as an additive for oils and bituminous coating materials such as road oils, asphalts, etc., to promote adherence to wet mineral aggregates, and to prevent or reduce the tendency of such materials to be stripped by water frommineral aggregates. The amount of the sulfonate composition to be used depends'upon several factors, among which are the type of oil or bituminous materials em ployed, the area of the aggregate-bitumen interface, the chraacteristics of the aggregate material, the severity of the conditions of use, etc. It will be appreciated that these factors, are interdependentto some extent, and that, therefore, the quantity. of .sulfonate composition which can be .used most advantageouly will be determined for the individual combinationof bitumen In general the amount of sulfonate composition used to produce the best effects should be sufficient to produce a bitumen composition. having fromabout 0.5 per cent to about 5 per cent, of the per cent metal sulfonate, based upon the bitumen used.

Set forth below, in Table I, are indi cating the efiectiveness of adjuncts prepared in accordance with the present invention as. compared to adjuncts prepared from total sludge without withdrawing a lower portion thereof. These data indicate the effect of such-adjuncts in a commercial paving operation i which. a mechanical paving machinewas employed to lay an actualstrip of highway. The. results. given are 9 the consensus of several experienced observers visual examination of the coated aggregate.

Percent coating retained after pouring water on freshly laid strip.

1 Paving asphalt containing 2% oi adjunct from total sludge.

I Paving asphalt containing 1% of adjunct from sludge from which lower 40% had been withdrawn prior to hydrolysis.

The amount of black acids which are present in a sulfuric acid sludge is dependent upon the type of oil treated and the amount and strength of sulfuric acid employed. The molecular weight and relative water solubility of the blaclrv acids are likewise affected by those factors. black acids may be found to some extent in practically every strata in a settled sludge, they are primarily found in the lower portions thereof. It has been found that at least 75 per cent of the black acids may be removed from most sludges by drawing off the lower 40 per cent thereof but it should be understood that in some sludges the black acids are such as to be more concentrated in the lowest portions of the sludge and, hence, substantially all of the black acids may be removed by drawing off an amount which is considerably less than 40 per cent of the total sludge. Thus, in accordance with the present invention, an amount of from about 10% to about 60% of the total sludge should be drawn off, preferably from about to about 50, before proceeding with the hydrolysis step.

In addition to the amount and characteristics of the black acids, the viscosity of acid sludge itself is dependent to a considerable extent upon the type of oil treated and the amount and strength of the sulfuric acid employed. The consistency of acid sludges vary from relatively fluid pumpable sludges of rather high viscosity to a semi-solid sludge which is essentially unpumpable. As is Well-known in the art, the viscosity of sulfuric acid sludges may be reduced by the addition thereto of sulfuric acid of from about 50 to about 100 per cent strength. It is often desirable, therefore, in accordance with the present invention, to mix such sulfuric acid with the sludge in order to increase the fluidity and aid the stratification of black acids.

Percentages given herein and in the appended claims are weight percentages unless otherwise stated.

We claim:

1. The method of preparing a stable homogeneous metal sulfonate-containing adjunct composition for bituminous material which comprises withdrawing a substantial portion from the bottom of a settled sulfuric acid sludge in order to remove most of the black acids present in said sludge, substantially freeing the remainin upper portion of said sludge from unreacted Whereas sulfuric acid, diluting the substantially sulfuric acid-free upper portion of said sludge with at least about 3 to about 5 volumes of water to each volume of sludge, adding to the diluted acid sludge portion a sufficient amount of a basicreacting, polyvalent-metal 'compound to neutralize the sulfonic acids therein, adding from about 25% to about of a liquid aromatic hydrocarbon having a boiling point of at least about 220 F., adjusting the water content to not more than 35% and adding from about 2% to about 15% of a alkanol.

2. The method of preparing a stable homogeneous metal sulfonate-containing adjunct composition for bituminous materials which comprises separating a. bottom portion of from 10 to about 60% from a settled sulfuric acid sludge, substantially freeing the remaining upper portion of said sludge from unreacted sulfuric acid, diluting the substantially sulfuric acid-free upper portion of said sludge with about 5 volumes of water to each volume of sludge, adding to the diluted acid sludge portion a sufficient amount of a basic-reacting, polyvalent-metal compound to neutralize the sulfonic acids therein; adding from about 25% to about 75% of a liquid aromatic hydrocarbon having a boiling point of at least 220 F., adjusting the water content to not more than 35%, and adding from about 2% to about 15% of alkanol.

3. In the method of preparing a stable homogeneous metal sulfonate-containing adjunct composition for bituminous materials which comprises substantially freeing a settled acid sludge from unreacted sulfuric acid, diluting the sulfuric acid free sludge with about 5 volumes of Water to each volume of sludge, adding sufficient basic-reacting, polyvalent-metal compound to the substantially sulfuric acid free sludge to neutralize the sulfonic acids therein, adding from about 25% to about 75% of a liquid aromatic hydrocarbon having a boiling point of at least about 220 F., adjusting the water content to no more than 35% and adding from about 2 to 15% of a alkanol thereto, the improvement which comprises discarding a bottom portion from about 10 to 60% from the settled acid sludge prior to the step of removing substantially all of the unreacted sulfuric acid therefrom, said discard of the bottom portion being elfective to eliminate from the sludge a substantial amount of the black acids initially present therein.

4. The method of claim 1 in which the aromatic hydrocarbon is an aromatic fraction boiling from about 400 F., to about 750 F., produced by the catalytic conversion of aliphatic hydrocarbons.

5. The method of claim 1 in which the alkanol is isopropyl alcohol.

6. The method of claim 1 in which the basic compound is an alkaline earth basic compound.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Merrill Dec. 11, 1928 OTHER REFERENCES Number 

1. THE METHOD OF PREPARING A STABLE HOMOGENEOUS METAL SULFONATE-CONTAINING ASJUNCTCOMPOSITION FOR BITUMINOUS MATERIAL WHICH COMPRISES WITHDRAWING A SUBSTANTIAL PORTION FROM THE BOTTOM OF A SETTLE SULFURIC ACID SLUDGE IN ORDER TO REMOVE MOST OF THE BLACK ACIDS PRESENT IN SAID SLUDGE, SUBSTANTIALLY FREEING THE REMAINING UPPER PORTION OF SAID SLUDGE FROM UNREACTED SULFURIC ACID, DILUTING THE SUBSTANTILLY SULFURIC ACID-FREE UPPER PORTION OF SAID SLUDGE WITH AT LEAST ABOUT 3 TO ABOUT 5 VOLUME OF WATER TO EACH VOLUME OF SLUDGE, ADDING TO THE DILUTE ACID SLUDGE PORTION A SUFFICIENT AMOUNT OF A BISICREACTING, POLYVALENT-METAL COMPOUND TO NEUTRALIZE THE SULFONIC ACIDS THEREIN, ADDING FROM ABOUT 25% TO ABOUT 75% OF A LIQUID AROMATIC HYDROCARBON HAVING A BOILING POINT OF AT LEAST ABOUT 220* F., ADJUSTING THE WATER CONTENT TO NOT MORE THAN 35% AND ADDING FROM ABOUT 2% TO ABOUT 15% OF A ALKANOL. 